Coagulation and settling of finely divided solids from aqueous suspensions thereof



United States Patent 3,492,225 COAGULATION AND SETTLING 0F FINELY DIVIDED SOLIDS FROM AQUEOUS SUSPEN- SIONS THEREOF John W. Ryznar, Burlington, Ontario, Canada, assignor to Nalco Chemical Company, Chicago, Ill., :1 corporation of Delaware No Drawing. Application June 19, 1961, Ser. No. 117,843, which is a division of application Ser. No. 341,367, Mar. 9, 1953. Divided and this application Nov. 2, 1966, Ser. No. 591,426

Int. Cl. B01d 21/01 U.S. Cl. 21054 6 Claims This application is a division of my copending application, Ser. No. 117,843, filed June 19, 1961, which is a division of Ser. No. 341,367, filed Mar. 9, 1953, now abandoned.

This invention relates to a method of coagulating and producing settling of finely divided solids which are predominantly inorganic and normally remain suspended in water, more particularly dilute suspensions in water containing concentrations within the range of about 003% to about 3% by weight of said solids.

One of the most difiicult industrial problems is to clarify industrial waste which would otherwise create a nuisance and cause pollution in lands and streams. Examples of such wastes are phosphate mine waters, coal washing waters, clay suspensions, calcium carbonate suspensions, and other suspensions of finely divided solids in water which result from industrial processes such as mining, washing, purification, and the like. These suspensions normally contain the solid materials in very finely divided form in concentrations within the range of about .003% to about 3% by weight of the suspension. Such suspensions will remain stable for days and many of them are not affected by the addition or ordinary coagulants such as alum. If the solids are allowed to remain in suspension the resultant suspension cannot be utilized for industrial processes and also presents a disposal problem.

One of the objects of the present invention is to provide a new and improved method for coagulating and producing settling of finely divided solids which are predominantly inorganic and normally remain suspended in water in concentrations of .003% to 3% by weight of the suspension.

Another object of the invention is to provide a method of treating suspensions of the type described with relatively small amounts of materials which will produce settling of the finely divided solids without any other harmful result. Other objects will appear hereinafter.

In accordance with the invention it has been found that it is possible to produce coagulation and settling of finely' divided solids which are predominantly inorganic and normally remain suspended in water in concentrations of .003% to 3% by weight of the suspension by treating said suspensions with about 1 to 15 parts per million based on the weight of the total suspension of a synthetic Water dispersible polymer having a weight average molecular weight of at least 10,000 and having a structure derived by the polymerization of at least one monoolefinic compound through the aliphatic unsaturated group, said structure being substantially free of crosslinking. The treating agents which have been found to be especially effective for the purpose of the invention are Water dispersible synthetic polymers having a linear hydrocarbon structure and containing in a side chain a hydrophilic group from the class consisting of carboxylic acid, carboxylic acid anhydride, carboxylic acid amide, hydroxy, pyridine, pyrrolidone, hydroxy alkyl ether, alkoxy, and carboxylic acid salt groups.

The treating agents which are eflective for the purpose "Ice of the invention fall in three classes, namely (1) those consisting of polymeric organic substances which in an aqueous medium will form organic anions having a substantial number of negative electrical charges distributed at a plurality of positions on the polymer; (2) those consisting of polymeric organic substances which in an aqueous medium will form organic cations having a substantial number of positive charges distributed at a plurality of positions on the polymer; and (3) those consisting of polymeric organic substances which in an aqueous medium will not form ions but nevertheless contain a suflicient number of hydrophilic groups to be water dispersible. The first class of materials is referred to herein as anionic organic polymers, the second class is referred to herein as cationic organic polymers, and the third class is referred to herein as non-ionic organic polymers. The first two classes can also be referred to as polyeletrolytes.

The term polyelectrolyte is intended to cover syn thetic organic polymers which in an aqueous medium will form organic ions having a substantial number of electrical charges distributed at a plurality of positions.

The synthetic organic polymers containing only carboxylic acid, carboxylic acid anhydride, and carboxylic acid salt groups in a side chain are anionic. The synthetic organic polymers containing only pyridine or other similar nitrogen containing nucleus are cationic. The synthetic organic polymers containing only a carboxylic acid amide, pyrrolidone, a hydroxy, a hydroxyalkyl ether and/or an alkoxy group in a side chain are non-ionic. The invention contemplates the employment of polymers which contain anionic, cationic and/or non-ionic groups. It also contemplates the employment of mixtures of 'anionic, cationic and/or non-ionic water dispersible synthetic organic polymers.

An important class of treating agents employed for the purpose of the invention consists of the synthetic polymeric water soluble polyelectrolytes having an average molecular weight greater than 10,000 which are copolymers of compounds containing the group and at least one other monoolefinic monomer. I

Another important class of treating agents employed for the purpose of the invention consists of synthetic water soluble polyelectrolytes having a weight average molecular weight of at least 10,000 which are polymers of a compound containing the molecular group H ($112M O wherein n is an integer trom zero (0) to one (1) inclusive.

The following water dispersible synthetic organic polymers and their characteristic grouping illustrate the types of polymers which have been found to be effective for the practice of the invention:

No. Name Characteristic Grouping 4. Polyvinyl methyl etlier- C HO H2CH-CH maleic anhydride. 1 I

- Methaerylic acid- C H CH methacrylamidc.

CHzO-CH2 O O C O NH: H(+) 6.- Polyacrylic acid. --0 H -(|3H- C O O H(+) 7. Isopropenyl acetate- CH maleic anhydride I sodium salt. CH2- (I3-(I3H([1H (I) (|]=O O=O O aC= 0 (5 C O O 8 Itaconic acidvinyl acetate.

TCOH2--CH2-CH CHzC 0 0 o H(+) CH C=O 9. Polyvinyl pyridine- CH CH hydrochloride.

mam 01M 10. 2-methyl styreuemaleic CH anhydride sodium salt. I

COH2OH (i211- COO() COO() Na(+) N a(+) 11. Pol vinyl pyrrolidone.

y (IJCH2 H2O (13:0 HgC-CH l2- Styrene-maleic. CH-CH -(I3H-(| H COO() COO() I Na Na 13- Polyvinyl alcohol. -CHCH2 14- Polyvinyl methyl ether. -CH-OHF 15. Methylmethacrylate- CH maleic anhydride (I; sodium salt. ong-on (EH- COOCHa COO() COO() 16--.- Polyvinyl acetate CH-CHz emulsion. I CHaC=O 17. Acrylic acid styrene CH-CHzCH-CH copolymer.

Any of the polyelectrolytes disclosed in United States Patent No. 2,625,529 can be employed for the purpose of the invention. Where the copolymer is derived from a polycarboxylic acid derivative and at least one other monomer copolymerizable therewith the polycarboxylic acid derivative may be maleic anhydride, maleic acid, fumaric acid, itaconic acid, aconitic acid, citraconic acid, the amides of these acids, the alkali metal (e.g. sodium, potassium and lithium), the alkaline earth metal (e.g. magnesium, calcium, barium and strontium), and ammonium salts of these acids, the partial alkyl esters (e.g. methyl, ethyl, propyl, butyl mono esters), the salts of said partial alkyl esters, and the substituted amides of these polycarboxylic acids. Where the hydrophilic maleic acid derivatives are used as one of the starting components to form the copolymer the hydrophobic comonomers may be, for example, styrene, alphamethylstyrene, vinyl toluene, chlorostyrenes, vinyl acetate, vinyl chloride, vinyl formate, vinyl alkyl ethers, alkyl arcrylates, alkyl methacrylates, ethylene, propylene, and/or isobutylene.

The foregoing synthetic copolymers are preferably obtained by reacting equimolar proportions of a polycarboxylic acid derivative and at least one other monomer but certain of the hydrophilic derivatives of unsaturated polycarboxylic acids can be polymerized in less than equimolar proportions with some of the less hydrophobic comonomers, for example, vinyl formate and vinyl acetate.

Some of the synthetic organic polymers and copolymers are more effective than others, the effectiveness being dependent in part upon the kind and number of said chain groupings in the particular polymer, the molecular Weight thereof, and the type of suspension being treated. In general, for effective results the polymer should have a relatively high molecular weight in excess of 10,000 and ordinarily within the range of 15,000 to 100,000.

The invention will be illustrated but is not limited by the following examples, in which the quantities are stated in parts by weight unless otherwise indicated.

EXAMPLE I The invention was evaluated on a phosphate mine water known as Bonny Lake hydroseparator overflow water containing 21,000 parts per million of suspended solids. Various types of polymers were added in varying proportions. A polymer corresponding to Formula No. 1 (Acrysol GS) was added at the rate of 0.5 part per million, 1.0 part per .million and 2.0 parts per million. Various dilutions of the Bonny Lake water with water were made and the following results were noted:

Susi ii 0 5 A l 1 A l 0 i p.p.m. cryso .0 p.p.m. cryso 2.0 p.p.m. Acrysol p.p.m. GS GS GS 21,000..- Little or no coagu- Beginning eoagula- Fair coagulation.

lation. tion.

5,200--.- Fair coagulation Good coagulation.-- Good coagulation.

1,300.... Good coagulation-.. Very good coagula- Very good coagulation. 300. do Do. do Do. Good coagulation Good coagulation. Fair c0agu1ation Fair coagulation. 40 Poor coagulation Poor coagulation. 30 N o coagulation N o coagulation.

20 do do Bonny Lake water containing 21,000 parts per million of suspended solids was treated with a compound corresponding to Formula No. 6 (Acrysol A-l) and very good coagulation was obtained at a dosage of 4 parts per million. A related compound (Orthocryl C) gave good coagulation at a dosage of 1 part per million.

EXAMPLE III EXAMPLE IV The Pauway No. 4 water was diluted and various amounts of sodium polyacrylate added with the following results:

Suspended Solids, 0.4 p.p.m. Acrysol 1.0 p.p.m. Acrysol 2.0 p.p.m. Acrysol p.p.m. GS GS GS 74 Good coagulation... Very good 'coagula- Very good coagulation. tion. 50 Fair coagulation Good coagulation-.- Good coagulation. 40 Poor to fair coagu- .-do Do.

lation. 30 Poor coagulation Falr coagulat1on Do. Lilttle or no coagu- Poor coagulation Fan" coagulation.

ation.

From these results it is noted that with this particular water in the concentrations of polymer employed the suspended solids in the water should be at least 20 parts per million before the treatment is effective.

EXAMPLE V The Bonny Lake hydroseparator overflow water containing 20,000 parts per million of suspended solids was adjusted to various pH values by adding small quantities of 1.0 normal hydrochloric acid solution or 1.0 normal sodium hydroxide solution. Sodium polyacrylate (Acrysol GS) was added in small increments with a period of stirring with each adjustment and the coagulation efiect on each test sample was observed. The results are summarized in the following table:

pH Acrysol GS Acrysol GS Acrysol GS 3.0 Fair coagulation Fair coagulation Fair coagulation.

due to acid. 4.1 Slight coagulation Poor coagulation.... Do.

due to acid. 5.1 do -do Fair to good coagulation. 6.0 No coagulation Fair coagulation Good coagulation. 6.7 Coagulation begin- Good coagulation. Very good coaguning. lation. 7.2 "do do Do. 7.9 do .d0 Do. 8.5 No coagulation No coagulation Coagulation beginnlng. No coagulation. Do. Do.

At pH values of 5.1 and below, a certain amount of coagulation was apparent before any sodium polyacrylate had been added. This coagulation due to acid was not very elfective and the size of the floc was very small. 'However, the acid coagulation resulted in a clearer water after the floc had settled than the water obtainable using sodium polyacrylate alone at a higher pH.

In a similar manner the Pauway No. 4 phosphate mine water was tested and excellent coagulation with sodium polyacrylate (Acrysol GS) in the pH range of 4.5 to 9.4 was obtained.

EXAMPLE VI Coagulation tests were made on water from the circulating system of the Franklin Coal Washer Plant, Bethlehem Steel Company, containing 18,800 parts per million of suspended solids which appeared to consist almost entirely of finely divided coal particles. The pH of this water was about 7.8. In the results given in the following table the settling times are given in terms of the minutes required for approximately 99% of the solids to precipitate after stirring was discontinued.

Settling Time,

Test Treatment Coagulation Minutes 1 None Poor 15 2 Sodium Polyacrylate (Acrysol Very good... 1

GS) 2 p.p.m.

EXAMPLE VII A sodium polymethacrylate polymer was tested and found to be a good coagulant for the Bonny Lake phosphate water at a dosage of 8 parts per million and for Pauway No. 4 water at a dosage of 1 part per million.

EXAMPLE VIII A maleic anhydride vinyl acetate polymer (Formula No. 3) was tested and found to be a good coagulant for the Pauway No. 4 phosphate mine water at a dosage of 1 part per million.

EXAMPLE IX Pauway No. 4 mine water was treated with a compound corresponding to Formula No. 5 and very good coagulation was obtained at a dosage of 1 part per million.

EXAMPLE X Pauway No. 4 phosphate mine water was treated with a compound corresponding to Formula No. 10 and cogulation was obtained at a dosage of 4 parts per million.

EXAMPLE XI Pauway No. 4 phosphate mine Water was treated with a compound corresponding to Formula No. 11 and good coagulation was obtained at a dosage of 4 parts per million.

EXAMPLE XII Pauway No. 4 phosphate mine water was treated with a compound corresponding to Formula No. 12 and good coagulation was obtained at a dosage of 1 part per million.

EXAMPLE XIII Pauway No. 4 phosphate mine water was treated with a compound corresponding to Formula No. 13 (high viscosity type A polyvinyl alcohol) and good coagulation was obtained at a dosage of 5 parts per million.

EXAMPLE XIV A coal suspension containing 2000 parts per million of suspended solids was treated with a compound corresponding to Formula No. 3 and coagulation was obtained at a dosage of 1 part per million.

EXAMPLE XV A coal suspension containing 2000 parts per million of solids was treated with a compound corresponding to Formula No. 4 and coagulation was obtained at a dosage of 5 parts per million.

EXAMPLE XVI A coal suspension containing 2000 parts per million of suspended solids was treated with a compound correspond ing to Formula No. 9 and good coagulation was obtained at a dosage of 1 part per million.

EXAMPLE XVII A synthetic water was prepared by adding bentonite to Chicago water in order to produce a suspension of 2000 parts per million of suspended solids. Good to very good coagulation of this suspension was obtained at a dosage of 1 part per million with each of the compounds corresponding to Formula Nos. 1 to 8. The compound corresponding to Formula No. 9 gave very good coagulation at a dosage of parts per million. The compound corresponding to Formula No. 10 gave fair coagulation at 1 part per million. The compound corresponding to Formula No. 11 gave good coagulation at 5 parts per million. The compound corresponding to Formula No. 12 gave fair coagulation at 5 parts per million. The compound corresponding to Formula No. 13 gave fair coagulation at 1 part per million. The compound corresponding to Formula No. 14 gave good coagulation at 5 parts per million. The compound corresponding to Formula No. 15 gave fair coagulation at 1 part per million. The compound corresponding to Formula No. 16 gave fair coagulation at 5 parts per million and very good coagulation at 15 parts per million. The compound corresponding to Formula No. 17 gave fair coagulation at 5 parts per million.

EXAMPLE XVIH A synthetic water was prepared containing 2000 parts per million of calcium carbonate in suspension in Chicago tap water. Very good coagulation of this water was obtained with sodium polyacrylate at a dosage of 5 parts per million. Fair to good coagulation of this water was obtained with a compound corresponding to Formula No. 4 at a dosage of 1 part per million. Good coagulation of this suspension was obtained with compounds corresponding to Formula No. 6 at a dosage of 1 part per million. Good coagulation of this suspension was obtained with compounds corresponding to Formula No. 9 at a dosage of 5 parts per million.

In a similar manner various types of synthetic polymers were tested and found to be effective in coagulating suspensions such as iron ore suspensions and carbonation juice in beet sugar processes. Sodium polyacrylate (Formula No. 1) and polymethyl ether maleic anhydride polymers (Formula No. 4) were found to be eifective in increasing the size and rate of settling of the floc of the second carbonation juice from a beet sugar manufacturing plant at concentrations of 2.5 and 5 parts per million respectively.

In general, the polymers employed in accordance with the invention appear to be particularly effective at a pH between about 4.5 and 9.5 and the optimum effectiveness in most cases is at a pH value between 6 and 8 particularly in coal washing waters and phosphate mine waters.

The invention is especially valuable in the clarification of high turbidity waters and in removing from suspension suspended solids which otherwise would be objectionable and would interfere with the disposal of various types of waste waters and wash waters from industrial processes. The use of the invention makes it possible to cause the settling of many diiferent types of solids from suspensions thereof at a higher rate than has heretofore been possible in many instances. The invention is also applicable to coagulating and producing settling of finely divided solids, many of which could not heretofore be coagulated by ordinary methods. Furthermore, the addition agents employed in the practice of the invention are effective in extremely small quantities and do not produce harmful contaminants.

The term synthetic organic polymer is employed herein to cover high molecular weight compounds made by building up the same molecule of a given monomer or by copolymerizing two or more different monomers. The term monoolefinic means that the monomer of monomers from which the polymer is derived contain a single double bond.

The invention is hereby claimed as follows:

1. A method of coagulating and producing settling of finely divided solids which are predominantly inorganic and normally remain suspended in water in concentrations of .003% to 3% by weight of the suspension which comprises treating said suspension with about 1 to 15 parts per million based on the weight of the total suspension of a synthetic polymer in a water dispersible state having a weight average molecular weight of at least 10,000 and having a linear hydrocarbon structure containing an alkoxy group in a side chain, and separating the resultant coagulated solids from suspension in said water.

2. A process as claimed in claim 1 in which the pH is 4.5 to 9.5.

3. A process as claimed in claim 1 in which said polymer also contains a carboxy group in a side chain.

4. A process as claimed in claim 1 in which said suspension is a phosphate mine water.

5. A process as claimed in claim 1 in which said suspension is a coal wash water.

6. A process as claimed in claim 1 in which the side chains of said polymer are composed solely of alkoxy groups.

References Cited UNITED STATES PATENTS 3,418,237 12/1968 Booth et a1. 2l054 MICHAEL E. ROGERS, Primary Examiner mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3392,25 Dated January 2'27 1910 Invenwfl m It is certified that error appears in the above-identified patent nnd thnt aid Letters Patent an hereby col-rand n lhmm below:

Cplumn 3, 1n the table, entry b, under "Characteristic Grouping", that portion of the formula reading I CHgCOO CH= Column 4, line 16, "arcrylates" ahoulc} read --acry1atea- Signed and sealed this 30th day of June 1970.

(SEAL) Attest:

EDWARD M.FLETCHER,JR.

WILLIAM E SCHUYLER, JR. Attesting Officer Commissioner of Patents 

1. A METHOD OF COAGULATING AND PRODUCING SETTLING OF FINELY DIVIDED SOLIDS WHICH ARE PREDOMINANTLY INORGANIC AND NORMALLY REMAIN SUSPENDED IN WATER IN CONCENTRATIONS OF .003% TO 3% BY WEIGHT OF THE SUSPENSION WHICH COMPRISES TREATING SAID SUSPENSION WITH ABOUT 1 TO 15 PARTS PER MILLION BASED ON THE WEIGHT OF THE TOTAL SUSPENSION OF A SYNTHETIC POLYMER IN A WATER DISPERSIBLE STATE HAVING A WEIGHT AVERAGE MOLECULAR WEIGHT OF AT LEAST 10,000 AND HAVING A LINEAR HYDROCARBON STRUCTURE CONTAINING AN ALKOXY GROUP IN A SIDE CHAIN, AND SEPARATING THE RESULTANT COAGULATED SOLIDS FROM SUSPENSION IN SAID WATER. 